EP0532099A1

EP0532099A1 - Improved process for selective hydrogenation of conjugated diene polymers

Info

Publication number: EP0532099A1
Application number: EP92202700A
Authority: EP
Inventors: Linda Rae Chamberlain; Carma Joleen Gibler
Original assignee: Shell Internationale Research Maatschappij BV
Current assignee: Shell Internationale Research Maatschappij BV
Priority date: 1991-09-09
Filing date: 1992-09-07
Publication date: 1993-03-17
Anticipated expiration: 2012-09-07
Also published as: BR9203462A; JP3152513B2; TW213925B; US5206307A; MX9205114A; ES2082349T3; DE69207524D1; EP0532099B1; CN1070412A; KR100253471B1; CN1050139C; JPH05194630A; KR930006058A; DE69207524T2; RU2093524C1

Abstract

There is provided an improved process for the hydrogenation of conjugated diene polymers which comprises polymerizing or copolymerizing at least one conjugated diene with an organo alkali metal polymerization initiator in a suitable solvent thereby creating a living polymer, terminating the polymerization by the addition of hydrogen and effecting selective hydrogenation of the double bonds in the conjugated diene units of the terminated polymer by contacting the polymer, in the absence of hydrocarbon lithium and alkoxy lithium compounds, with hydrogen in the presence of at least one bis(cyclopentadienyl)titanium compound. The improvement is the use of alkyl benzoate as a promoter in the hydrogenation step. Methyl benzoate is the most preferred promoter.

Description

The present invention relates to an improved process for the production of selectively hydrogenated polymers of conjugated dienes utilizing a titanium hydrogenation catalyst and more particularly to the use of a new hydrogenation catalyst promoter.
The hydrogenation or selective hydrogenation of conjugated diene polymers has been accomplished using any of the several hydrogenation processes known in the prior art. For example the hydrogenation has been accomplished using methods such as those taught, for example, in U.S. Patent Nos. 3,494,942; 3,634,594; 3,670,054 and 3,700,633 and Re. 27,145. These methods known in the prior art for hydrogenating polymers containing ethylenic unsaturation and for hydrogenating or selectively hydrogenating polymers containing aromatic and ethylenic unsaturation, involve the use of a suitable catalyst, particularly a catalyst or catalyst precursor comprising a Group VIII metal.
In the methods described in the foregoing patents, a catalyst is prepared by combining a Group VIII metal, particularly nickel or cobalt, compound with a suitable reducing agent such as an aluminium alkyl. Also, while aluminium alkyls are the preferred reducing agents, it is known in the prior art that alkyls and hydrides of metals of Groups I-A, II-A and III-B of the Periodic Table of the Elements are effective reducing agents, particularly lithium, magnesium and aluminium. In general, the Group VIII metal compound is combined with Group I-A, II-A or III-B metal alkyl or hydride at a concentration sufficient to provide Group I-A, II-A and/or III-B metal to Group VIII metal ratios within the range of from 0.1:1 to 20:1, preferably from 1:1 to 10:1. As indicated in the before-mentioned U.S. patents, the hydrogenation catalyst is generally prepared by combining the Group VIII metal compound and the reducing agent in a suitable solvent or diluent at a temperature within the range of from 20°C to 60°C before the catalyst is fed to the hydrogenation reactor.
U.S. Patent 4,501,857 disclosed selective hydrogenation of the double bonds in conjugated diene polymers by hydrogenating such polymers in the presence of at least one bis(cyclopentadienyl)titanium compound and at least one hydrocarbon lithium compound wherein the hydrocarbon lithium compound can be an added compound or a living polymer having a lithium atom in the polymer chain. U.S. Patent 4,980,421 disclosed that similar hydrogenation activity can be accomplished with the same titanium compounds in combination with an alkoxy lithium compound which can either be added directly or as a reaction mixture of an organo lithium compound with an alcoholic or phenolic compound. The use of these catalyst systems was said to be advantageous because the catalysts were said to be highly active so that they were effective even in such a small amount as not to affect adversely the stability of a hydrogenated polymer and require no deashing step. Further, the hydrogenation was said to be able to be carried out under mild conditions.
In U.S. Patent 4,673,714, bis(cyclopentadienyl)titanium compounds were disclosed which preferentially hydrogenate the double bonds of conjugated dienes but do not require the use of an alkyl lithium compound. These titanium compounds were bis(cyclopentadienyl)titanium diaryl compounds. The elimination of the need for the hydrocarbon lithium compound was said to be a significant advantage.
U.S. patent 5,039,755 disclosed a process for the hydrogenation of conjugated diene polymers which first involves the polymerization or copolymerization of such monomers with an organo alkali metal polymerization initiator in a suitable solvent thereby creating a living polymer. The living polymer is terminated by the addition of hydrogen. Finally, selective hydrogenation of the double bonds in the conjugated diene units of the terminated polymer is carried out in the presence of at least one bis(cyclopentadienyl)titanium compound preferably of the formula:

wherein R₁ and R₂ are the same or different and are selected from the group consisting of halogen groups, C₁-C₈ alkyl and alkoxy groups, C₆-C₈ aryloxy groups, aralkyl, cycloalkyl groups, silyl groups and carbonyl groups. The hydrogenation step is carried out in the absence of hydrocarbon lithium and alkoxy lithium compounds.
The present invention provides an improvement upon the process described in the above U.S. patent No. 4,039,755. The improvement is the utilization in the hydrogenation step of alkyl benzoate as a promoter to enhance the hydrogenation of the polymer. Alkyl benzoate boosts the activity of the titanium catalyst and generally results in more extensive saturation of the diene segments of the polymer. Accordingly, the present invention relates to a process for the hydrogenation of conjugated diene polymers which comprises:

(a) polymerizing or copolymerizing at least one conjugated diene with an organo-alkali metal polymerization initiator in a suitable solvent thereby creating a living polymer,
(b) terminating the polymerization by the addition of H₂, and
(c) selectively hydrogenating the double bonds in the conjugated diene units of said terminated polymer by contacting the polymer, in the absence of hydrocarbon lithium and alkoxy lithium compounds, with hydrogen in the presence of at least one bis(cyclopentadienyl)titanium compound of the formula:
wherein R₁ and R₂ are the same or different and are selected from the group consisting of halogen groups, C₁-C₈ alkyl and alkoxy groups, C₆-C₈ aryloxy groups, aralkyl, cycloalkyl groups, silyl groups and carbonyl groups, characterized in that alkyl benzoate is used as a promoter in step (c) to enhance the hydrogenation of the polymer.

The alkyl benzoate preferably is a C₁-C₅ alkyl benzoate, while methyl benzoate is most preferred.
The most advantageous range of operation is when the molar ratio of titanium to alkyl benzoate is from 1:1 to 6:1.
Figure 1 depicts the percent conversion versus time of the hydrogenation of a polystyrene-polybutadiene-polystyrene block copolymer of molecular weight 50,000 with and without the addition of methyl benzoate.
Figure 2 depicts the percent conversion versus time of the hydrogenation of a polystyrene-polyisoprene block copolymer of molecular weight 100,000 with and without the addition of methyl benzoate.
As is well known, polymers containing both aromatic and ethylenic unsaturation can be prepared by copolymerizing one or more polyolefins, particularly a diene, by themselves or with one or more alkenyl aromatic hydrocarbon monomers. The copolymers may, of course, be random, tapered, block or a combination of these, as well as linear, star or radial.
As is well known, polymers containing ethylenic unsaturation or both aromatic and ethylenic unsaturation may be prepared using anionic initiators or polymerization catalysts, such as organolithium compounds. Such polymers may be prepared using bulk, solution or emulsion techniques. In any event, the polymer containing at least ethylenic unsaturation will, generally, be recovered as a solid such as a crumb, a powder, a pellet or the like. Polymers containing ethylenic unsaturation and polymers containing both aromatic and ethylenic unsaturation are commercially available from several suppliers.
Conjugated dienes which may be polymerized anionically include those conjugated dienes containing from 4 to 12 carbon atoms, such as 1,3-butadiene, isoprene, piperylene, methylpentadiene, phenylbutadiene, 3,4-dimethyl-1,3-hexadiene, 4,5-diethyl-1,3-octadiene and the like. Conjugated dienes containing from 4 to 8 carbon atoms are preferred and butadiene is most preferred for use in such polymers. Alkenyl aromatic hydrocarbons which may be copolymerized include vinyl aryl compounds such as styrene, various alkyl-substituted styrenes, alkoxy-substituted styrenes, 2-vinyl pyridine, 4-vinyl pyridine, vinyl naphthalene, alkyl-substituted vinyl naphthalenes and the like.
If the block copolymer is prepared by a solution technique, any of the solvents known in the prior art to be useful in the preparation of such polymers may be used. Suitable solvents, then, include straight- and branched-chain hydrocarbons such as pentane, hexane, heptane, octane and the like, as well as, alkyl-substituted derivatives thereof; cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane and the like, as well as, alkyl-substituted derivatives thereof; aromatic and alkyl-substituted derivatives thereof; aromatic and alkyl-substituted aromatic hydrocarbons such as benzene, naphthalene, toluene, xylene and the like; hydrogenated aromatic hydrocarbons such as tetralin, decalin and the like; linear and cyclic ethers such as methyl ether, methyl ethyl ether, diethyl ether, tetrahydrofuran and the like.
Conjugated diene polymers and conjugated diene-alkenyl aromatic copolymers which may be used in the present invention include those copolymers described in U.S. Patents Nos. 3,135,716; 3,150,209; 3,496,154; 3,498,960; 4,145,298 and 4,238,202, the disclosure of which patents are herein incorporated by reference. Conjugated diolefin-alkenyl aromatic hydrocarbon copolymers which may be used in this invention also include block copolymers such as those described in U.S. Patent Nos. 3,231,635; 3,265,765 and 3,322,856. Polymers which may be treated in accordance with this invention also include coupled and radial block copolymers such as those described in U.S. Patent Nos. 4,033,888; 4,077,893; 4,141,847; 4,391,949 and 4,444,953. The radial polymers may be symmetric or asymmetric.
In the production of all types of polymers described above, the polymerization is terminated by utilizing hydrogen gas instead of the conventionally used alcohol terminating agent. The living polymer, or more accurately, the living end of the polymer chain, is terminated by the addition of hydrogen thereto. The theoretical termination reaction is shown using an S-B-S block copolymer for exemplary purposes:

S-B-S⁻Li⁺ + H₂ → S-B-SH + LiH

As shown above, it is theorized that lithium hydride is formed during the termination process. Formed in this manner, it is not a reactive polymerization initiator. It is inert to polymerization and does not interfere with the molecular weight control of the next polymerization batch as alcohol can.
It is usually advisable to contact and vigorously mix the gas with the polymerization solution at the end of the polymerization reaction. This contact and vigorous mixing can be effected by adding the hydrogen gas through spargers in a mixing vessel containing polymer solution. The time of contact should be at least 10 seconds and preferably 20 minutes to allow sufficient contact time for the reaction to occur. This primarily depends upon the efficiency of the gas contacting equipment, gas solubility, solution viscosity and temperature. Alternatively, a continuous system could be employed whereby hydrogen is pumped into a solution prior to going to a statically mixed plug flow reactor. Hydrogen could also be dissolved in an appropriate solution and added to the polymer solution to be terminated. Another method would be to cause the hydrogen to be absorbed into an absorption bed and then cause the polymer solution to flow through the absorption bed. The hydrogen contact could also be carried out by adding a material which gives off hydrogen upon decomposition, i.e. diimide.
When hydrogen is used, the problems of using alcohol, i.e. the formation of lithium alkoxides and excess alcohol impurities, are avoided. Furthermore, this process has been found to have significant advantage if the polymer made is to be hydrogenated. It has been found that if the present method is used, a bis(cyclopentadienyl)titanium hydrogenation catalyst may be used without the necessity of a hydrocarbon lithium or alkoxy lithium promoter, whether added with the catalyst or present in the living polymer.
As stated above, the hydrogenation step of the present process is carried out in the presence of a bis(cyclopentadienyl)titanium compound of the formula:

wherein R₁ and R₂ are the same or different and are selected from the group consisting of halogen groups, C₁-C₈ alkyl and alkoxy groups, C₆-C₈ aryloxy groups, aralkyl, cycloalkyl groups, silyl groups and carbonyl groups. The hydrogenation step is carried out in the absence of hydrocarbon lithium and alkoxy lithium compounds.
Specific bis(cyclopentadienyl) compounds (these compounds are also sometimes referred to as titanocenes) which may be used in the present invention include bis(cyclopentadienyl)titanium dichloride, bis(cyclopentadienyl)titanium dibromide, bis(cyclopentadienyl)titanium diiodide, bis(cyclopentadienyl)titanium difluoride, bis(cyclopentadienyl)titanium dicarbonyl, bis(cyclopentadienyl)titanium dimethyl, bis(cyclopentadienyl)titanium diethyl, bis(cyclopentadienyl)titanium dibutyl (including n-butyl, sec-butyl, tert-butyl), bis(cyclopentadienyl)titanium bis(trimethylsilylmethyl), bis(cyclopentadienyl)titanium dibenzyl, bis(cyclopentadienyl)titanium dihexyl, bis(cyclopentadienyl)titanium dimethoxide, bis(cyclopentadienyl)titanium diethoxide, bis(cyclopentadienyl)titanium dibutoxide, bis(cyclopentadienyl)titanium dipentoxide, bis(cyclopentadienyl)titanium dineopentoxide, bis(cyclopentadienyl) titanium diphenoxide, and all mixtures thereof. The preferred titanium compound is bis(cyclopentadienyl)titanium dichloride because of ease of handling, air stability and commercial availability.
The process according to the invention selectively hydrogenates conjugated dienes without hydrogenating alkenyl aromatic hydrocarbons to any degree. Hydrogenation percentages of greater than 50% are easily obtained, but it has been found that in order to achieve hydrogenation percentages of greater than 95% as is often desired, the alkali metal (for example, lithium) to titanium ratio must be at least 2:1 and preferably is in the range of from 3:1 to 30:1, because there has to be sufficient alkali metal to ensure quick and sufficient interaction between the two metals. A high viscosity (high molecular weight) polymer may require a higher ratio because of the lesser mobility of the metals in the polymer cement. If alkali metal hydride must be added to increase the ratio, it can be made in situ by adding an organo alkali metal compound and hydrogen to the polymer (e.g. by sparging), either before or after termination of the polymerization.
The above process is improved and the hydrogenation of the polymer is enhanced by the use of alkyl benzoate, preferably C₁-C₅ alkyl benzoate and most preferably methyl benzoate, as a promoter during the hydrogenation step. Alkyl benzoate may be added directly to the polymer solution prior to catalyst addition as a neat substance, but it is preferred that the alkyl benzoate is diluted in cyclohexane because of the low amounts of alkyl benzoate being added. Alkyl benzoate boosts the activity of the titanium catalyst and generally results in more extensive saturation of the diene segments of the polymer. Also, in many cases, the catalyst loading level may be reduced. This is advantageous because of cost factors and because there will be a lower amount of catalyst residue in the polymer. The advantages are illustrated by Figures 1 and 2 wherein olefin conversion improvements can be seen for respectively polybutadiene and polyisoprene based block copolymers, using methyl benzoate as the promoter.
In general, the hydrogenation is carried out in a suitable solvent at a temperature within the range of from 0° to 120°C, preferably 60 to 90°C, and at a hydrogen partial pressure within the range of from 1 bar (1 psig) to 84 bar (1200 psig), preferably from 8 to 15 bar (100 to 200 psig). Catalyst concentrations within the range of from 0.01 mmol (millimoles) per 100 grams of polymer to 20 mmol per 100 grams of polymer, preferably 0.04 to 1 mmol catalyst per 100 grams of polymer, are generally used and contacting at hydrogenation conditions is generally continued for a period of time within the range from about 30 to about 360 minutes. It is preferred that the alkyl benzoate is used in a molar ratio of titanium to alkyl benzoate in the range of from 1:1 to 6:1, because operating outside this range results in a decrease in ultimate olefin conversion. Suitable solvents for hydrogenation include, among others, n-heptane, n-pentane, tetrahydrofuran, cyclohexane, toluene, hexane and benzene. Because of the small amount of catalyst present in the polymer after hydrogenation, it is not necessary to separate the hydrogenation catalyst and catalyst residue from the polymer. However, if separation is desired, it may be carried out using methods well known in the prior art. Hydrogenation may be carried out in other manners such as batch processes, continuous processes, and semi-continuous processes.
The preparation of starting terminated polymer took place as follows:
A polystyrene-polybutadiene-polystyrene block copolymer of 50,000 molecular weight was prepared by anionic polymerization using sec-butyl lithium as the initiator. The polymerization took place in a mixture of cyclohexane and diethyl ether. The resulting polymer solution contained 20% by weight of polymer. The polymerization was terminated by sparging the polymer solution with hydrogen gas for approximately 30 minutes. This generated the cocatalyst for the hydrogenation reaction, i.e. LiH. For all of the following examples of hydrogenation of polymers, this feedstock was used as is.

Comparative Example 1

1560 grams of the polymer solution was pressure transferred to a 4-litre autoclave reactor. The amount of LiH present in the polymer solution was calculated to be 6.4 mmol. The polymer solution was stirred at 630 rpms (rotations per minute) for approximately 30 minutes, during which time it was also heated to 90°C. At this time, 0.125 mmol of bis(cyclopentadienyl)titanium dichloride suspended in 30 ml of cyclohexane, was added to the reactor. After catalyst addition, the reactor was pressurized to 28.6 bar (400 psig) hydrogen and the reactor temperature was maintained at 90°C. The hydrogenation reaction was allowed to proceed for three hours. The final conversion of the olefin was 74.0%, i.e. 74.0% of the aliphatic double bonds in the diene block were saturated.

Example 1

1560 grams of 20% by weight polymer solution was pressure transferred to a 4-litre autoclave reactor. The amount of LiH present in the polymer solution was calculated to be 6.4 mmol. To the polymer solution was added 0.75 mmol of methyl benzoate. The solution was stirred at 630 rpms for approximately 30 minutes, during which time it was also heated to 90°C. At this time, 0.125 mm of bis(cyclopentadienyl)titanium dichloride, suspended in 30 ml of cyclohexane, was added to the reactor. After catalyst addition, the reactor was pressurized to 28.6 bar (400 psig) hydrogen and the reactor temperature was maintained at 90°C. The hydrogenation reaction was allowed to proceed for three hours. The final conversion of the olefin was 98.7%. Thus, the methyl benzoate promoted system achieved much higher conversion.

Comparative Example 2

1560 grams of a 20% by weight polymer solution was pressure transferred to a 4-litre autoclave reactor. The amount of LiH present in the polymer solution was calculated to be 6.4 mmol. The polymer solution was stirred at 905 rpms for approximately 30 minutes, during which time it was also heated to 70°C. At this time, 0.25 mmol bis(cyclopentadienyl)titanium dichloride, suspended in 30 ml of cyclohexane, was added to the reactor. After catalyst addition, the reactor was pressurized to 10.7 bar (140 psig) hydrogen and the reactor temperature was maintained at 70°C. The hydrogenation reaction was allowed to proceed for three hours. The final conversion of the olefin was 90.6%.

Example 2

1560 grams of a 20% by weight polymer solution was pressure transferred to a 4-litre autoclave reactor. The amount of LiH present in the polymer solution was calculated to be 6.4 mmol. To the polymer solution was added 0.58 mmol methyl benzoate. The polymer solution was stirred at 905 rpms for approximately 30 minutes, during which time it was also heated to 70°C. At this time, 0.25 mmol bis(cyclopentadienyl)titanium dichloride, suspended in 30 ml of cyclohexane, was added to the reactor. After catalyst addition, the reactor was pressurized to 10.7 bar (140 psig) hydrogen and the reactor temperature was maintained at 70°C. The hydrogenation reaction was allowed to proceed for three hours. The final conversion of the olefin was 98.7%. Again, the methyl benzoate promoted system achieved a higher conversion under the same conditions.

Example 3 (Examples 3 and 4 demonstrate the effect of differing levels of methyl benzoate addition)

1560 grams of a 20% by weight polymer solution was pressure transferred to a 4-litre autoclave reactor. The amount of LiH present in the polymer solution was calculated to be 6.4 mmol. To the polymer solution was added 0.50 mmol methyl benzoate. The polymer solution was stirred at 850 rpms for approximately 30 minutes, during which time it was also heated to 75°C. At this time, 0.33 mmol of bis(cyclopentadienyl)titanium dichloride, suspended in 30 ml of cyclohexane, was added to the reactor. After catalyst addition, the reactor was pressurized to 17.6 bar (240 psig) hydrogen and the reactor temperature was maintained at 70°C. The hydrogenation reaction was allowed to proceed for three hours. The final conversion of the olefin was 98.8%.

Example 4

1560 grams of a 20% by weight polymer solution was pressure transferred to a 4-litre autoclave reactor. The amount of LiH present in the polymer solution was calculated to be 6.4 mmol. To the polymer solution was added 0.75 mmol methyl benzoate. The polymer solution was stirred at 850 rpms for approximately 30 minutes, during which time it was also heated to 75°C. At this time, 0.33 mmol bis(cyclopentadienyl)titanium dichloride, suspended in 30 ml of cyclohexane, was added to the reactor. After catalyst addition, the reactor was pressurized to 17.6 bar (240 psig) hydrogen and the reactor temperature was maintained at 70°C. The hydrogenation reaction was allowed to proceed for three hours. The final conversion of the olefin was 99.3%. For this example, an increase in the amount of methyl benzoate appears to have resulted in increased conversion at the same conditions.

Claims

A process for the hydrogenation of conjugated diene polymers which comprises:
(a) polymerizing or copolymerizing at least one conjugated diene with an organo-alkali metal polymerization initiator in a suitable solvent thereby creating a living polymer,

(b) terminating the polymerization by the addition of H₂, and

(c) selectively hydrogenating the double bonds in the conjugated diene units of said terminated polymer by contacting the polymer, in the absence of hydrocarbon lithium and alkoxy lithium compounds, with hydrogen in the presence of at least one bis(cyclopentadienyl)titanium compound of the formula:
wherein R₁ and R₂ are the same or different and are selected from the group consisting of halogen groups, C₁-C₈ alkyl and alkoxy groups, C₆-C₈ aryloxy groups, aralkyl, cycloalkyl groups, silyl groups and carbonyl groups, characterized in that alkyl benzoate is used as a promoter in step (c) to enhance the hydrogenation of the polymer.
The process of claim 1 wherein the alkyl benzoate is a C₁-C₅ alkyl benzoate.
The process of claim 2 wherein the C₁-C₅ alkyl benzoate is methyl benzoate.
The process of any one of the claims 1 to 3 wherein the molar ratio of titanium to alkyl benzoate is in the range of from 1:1 to 6:1.
The process any one of the claims 1 to 4 wherein the hydrogenation is carried out at a temperature within the range of from 0°C to 120°C and at a hydrogen partial pressure within the range of from 1 bar (1 psig) to 84 bar (1200 psig) and the catalyst concentration is within the range of from 0.01 mmol to 20 mmol of titanium per 100g of polymer and the contacting takes place for a period of time within the range of from 30 to 360 minutes.
The process of claim 5 wherein the hydrogenation is carried out at a temperature within the range of from 60-90°C and at a pressure within the range of from 8 to 15 bar (100 to 200 psig) and the catalyst concentration is within the range of from 0.04 to 1.0 mmol titanium per 100 g of polymer.
The process of any one of the claims 1 to 6 wherein the titanium compound is bis(cyclopentadienyl)titanium dichloride.
The process of claim 1 wherein the alkali metal:titanium metal ratio during the hydrogenation is at least 2:1.
The process of claim 8 wherein alkali metal hydride is added to the polymer to be hydrogenated by adding an organo alkali metal compound and hydrogen to the polymer prior to addition of the hydrogenation catalyst.
The process of any one of the claims 1-9 wherein the conjugated diene is butadiene.